Table Of ContentSmart Sensors, Measurement and Instrumentation 35
Md Eshrat E. Alahi
Subhas Chandra Mukhopadhyay
Smart
Nitrate
Sensor
Internet of Things Enabled Real-Time
Water Quality Monitoring
Smart Sensors, Measurement
and Instrumentation
Volume 35
Series Editor
Subhas Chandra Mukhopadhyay
School of Engineering
Macquarie University
Sydney, NSW
Australia
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Md Eshrat E. Alahi
(cid:129)
Subhas Chandra Mukhopadhyay
Smart Nitrate Sensor
Internet of Things Enabled Real-Time Water
Quality Monitoring
123
Md EshratE. Alahi SubhasChandra Mukhopadhyay
Shenzhen Institute of Advanced Schoolof Engineering
Technology,Chinese Academy ofSciences MacquarieUniversity
Shenzhen University Town Sydney,NSW,Australia
Shenzhen
Guangdong,China
ISSN 2194-8402 ISSN 2194-8410 (electronic)
Smart Sensors, Measurement andInstrumentation
ISBN978-3-030-20094-7 ISBN978-3-030-20095-4 (eBook)
https://doi.org/10.1007/978-3-030-20095-4
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Preface
Nitrate-Nisanaturallyoccurringioniccompoundthatisapartofnature’snitrogen
cycle.Nitrate-Narereadilylosttogroundandsurfacewaterasaresultofintensive
agriculture, industrial wastes, and disposal of human and animal sewage. The
impactofelevatednitrate-Nconcentrationsonwaterqualityhasbeenidentifiedasa
critical issue of a healthy environment for the future. Presently, water quality
managers follow the traditional measurement systems that involve physically col-
lecting thesamplingwater fromremotesites andtesting itinthelaboratory.These
methodsareexpensive,requiretrainedpeopletoanalysethedataandproducemuch
chemical waste.
Therefore, low-cost ion-imprinted polymer (IIP)-coated impedimetric nitrate-N
sensor was developed, and the detection range of nitrate-N was 1–10 (mg/L). The
selectiveIIPmaterialwassensitivetonitrate-Nionsinanaqueousmedium,andthe
results are validated through standard UV spectrometric methods. Micro-
electromechanical system (MEMS)-based interdigital sensor and sensing system
was also developed to measure nitrate-N, and the range was 0.01–0.5 (mg/L). The
graphite/PDMS-based low-cost sensor was also fabricated, and the sensor was
characterized to measure nitrate-N in the range of 1–70 (mg/L). Temperature
compensation was added for both the sensors (MEMS and graphene), and Wi-fi
connectivity was provisioned in the system to transfer the measured data in real
time. An improved LoRa-based sensing system (solar-panel- and rechargeable-
battery-powered) was developed and trialled in the field successfully which can
measure the nitrate-N concentration in real time and transfer the data to IoT cloud
server to overcome the limitations of laboratory-based sensing system.
Chapter 1 discusses the background and the introduction of the research. The
importance of nitrate sensor and in-situ-based sensing system with real-time
monitoring has been discussed. There are varieties of detection methods available
fornitrate.Someofthemarelaboratory-based,andsomeofthemcanbeusedinthe
sampling locations. The advantages and shortcomings of those methods are dis-
cussed in Chap. 2. Chapter 3 discusses the principle of interdigital capacitive
sensor,andthedetectionmethodofelectrochemicalimpedancespectroscopy(EIS).
Chapter 4 discusses the low-range nitrate measurement, the temperature
v
vi Preface
compensation technique which is employed in the developed sensor and the elec-
tronics of the IoT-enabled smart sensing system. Chapters 5, 6 and 7 discuss the
varieties of the sensor and their fabrication technique, validation methods and
development of the in situ IoT-enabled sensing system. Chapter 8 discusses the
conclusion of the research, limitations of the current research and prospects.
This book is originated from a Ph.D. research done at Macquarie University,
NSW, Australia. The aim of this work is to develop low-cost IoT-enabled smart
nitrate sensor for the detection of nitrate as contamination in natural water. The
authors are highly grateful to the colleagues who had a significant contribution to
thiswork:Dr.AnindyaNag,Dr.NasrinAfsarimanesh,Dr.KrishanthiJayasundera,
Dr. Keith Imrie, Dr. Fahmida Wazed Tina and Van Nguyen Thi Phuoc. Special
thanks to Macquarie University, Australia, and Massey University, New Zealand,
for providing research facilities. We would also extend our thanks to our families
for their support, motivation and encouragement throughout the work.
Shenzhen, China Dr. Md Eshrat E. Alahi
Sydney, Australia Prof. Subhas Chandra Mukhopadhyay
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2 Literature Review . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.2 Detection Methodologies. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.3 Electrochemical Detection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.4 Potentiometric Detection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
2.5 Amperometric Detection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
2.6 Voltammetric Detection. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.7 Chromatography Detection . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.8 Biosensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
2.9 Flow-Injection Analysis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
2.10 Electromagnetic Sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
2.10.1 Planar Electromagnetic Sensor . . . . . . . . . . . . . . . . . . . 20
2.10.2 Planar Interdigital Sensor . . . . . . . . . . . . . . . . . . . . . . . 22
2.11 Fibre-Optic Sensor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
2.12 Commercial Sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
2.13 Challenges and Future Opportunities . . . . . . . . . . . . . . . . . . . . . 28
2.14 Internet of Things (IoT). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
2.15 Existing Sensor Nodes for IoT. . . . . . . . . . . . . . . . . . . . . . . . . . 31
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
3 Interdigitated Senor and Electrochemical Impedance
Spectroscopy (EIS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
3.2 Planar Interdigital Sensors. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
3.3 Novel Planar Interdigital Sensors . . . . . . . . . . . . . . . . . . . . . . . . 45
3.4 Electrochemical Impedance Spectroscopy (EIS) . . . . . . . . . . . . . 46
vii
viii Contents
3.4.1 Basic Principles of EIS. . . . . . . . . . . . . . . . . . . . . . . . . 47
3.4.2 Data Representation in Nyquist Plot and Bode Plot . . . . 48
3.4.3 Randle’s Electrochemical Cell Equivalent Circuit
Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
3.5 Chapter Summary. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
4 Temperature Compensation for Low Concentration Nitrate
Measurement. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
4.2 Experimental Setup. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
4.2.1 MEMS-Based Sensor . . . . . . . . . . . . . . . . . . . . . . . . . . 54
4.2.2 Temperature Measurement . . . . . . . . . . . . . . . . . . . . . . 55
4.2.3 Nitrate Measurement. . . . . . . . . . . . . . . . . . . . . . . . . . . 55
4.3 Sensing System. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
4.3.1 Block Diagram of the Sensing System. . . . . . . . . . . . . . 57
4.3.2 The Signal Generator . . . . . . . . . . . . . . . . . . . . . . . . . . 57
4.3.3 Frequency Response Analysis Circuit . . . . . . . . . . . . . . 58
4.3.4 Controlling of Pump and Solenoid Valve. . . . . . . . . . . . 60
4.3.5 IoT-Based Smart System. . . . . . . . . . . . . . . . . . . . . . . . 61
4.4 Results and Discussions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
4.4.1 Measurement of Temperature . . . . . . . . . . . . . . . . . . . . 62
4.4.2 Nitrate Measurement and Standard Equation
Development . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
4.4.3 Stream Water Testing. . . . . . . . . . . . . . . . . . . . . . . . . . 68
4.4.4 Data in Cloud Server . . . . . . . . . . . . . . . . . . . . . . . . . . 68
4.4.5 Comparison of Impedance Measurement
by LCR and the Developed System. . . . . . . . . . . . . . . . 69
4.4.6 Improvement of Temperature Compensation . . . . . . . . . 71
4.5 Chapter Summary. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
5 Graphite/PDMS Capacitive Sensor for Nitrate Measurement . . . . . . 73
5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
5.2 Fabrication of the Printed Sensors . . . . . . . . . . . . . . . . . . . . . . . 73
5.3 Experimental Setup. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
5.4 Comparative Analysis of Two Different Sensors. . . . . . . . . . . . . 79
5.5 Temperature and Nitrate-N Measurement . . . . . . . . . . . . . . . . . . 79
5.6 IoT-Enabled Smart Sensing System . . . . . . . . . . . . . . . . . . . . . . 80
5.7 Results and Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
Contents ix
5.7.1 Comparative Analysis. . . . . . . . . . . . . . . . . . . . . . . . . . 81
5.7.2 Nitrate Measurement. . . . . . . . . . . . . . . . . . . . . . . . . . . 83
5.7.3 Temperature Measurement . . . . . . . . . . . . . . . . . . . . . . 83
5.8 Summarize . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
6 Preparation and Characterization of the Selectivity Material of
Nitrate Sensor. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
6.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
6.2 Ion Imprinting Polymerisation . . . . . . . . . . . . . . . . . . . . . . . . . . 91
6.2.1 Types of Imprinting Process . . . . . . . . . . . . . . . . . . . . . 92
6.2.2 Monomers, Cross-Linkers, Solvents and Initiator
for the Imprinting Procedure . . . . . . . . . . . . . . . . . . . . . 93
6.3 Polymerisation Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
6.3.1 Bulk Polymerisation . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
6.3.2 Precipitation Polymerisation . . . . . . . . . . . . . . . . . . . . . 95
6.3.3 Suspension Polymerisation . . . . . . . . . . . . . . . . . . . . . . 95
6.3.4 Surface (Emulsion) Polymerisation . . . . . . . . . . . . . . . . 95
6.4 Materials and Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
6.4.1 Chemicals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
6.4.2 Apparatus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
6.4.3 Synthesis of Nitrate Imprinted Polymer Coating. . . . . . . 96
6.4.4 Functionalizing the Polymer Coating. . . . . . . . . . . . . . . 98
6.4.5 Sorption Study. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
6.4.6 Static Sorption Time. . . . . . . . . . . . . . . . . . . . . . . . . . . 99
6.4.7 Selectivity Test. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
6.4.8 A Binding Procedure of Coated Sensor . . . . . . . . . . . . . 99
6.4.9 EIS Measurement of the Coated Sensor. . . . . . . . . . . . . 100
6.4.10 Unknown Sample Measurement . . . . . . . . . . . . . . . . . . 101
6.4.11 Reusability Testing. . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
6.4.12 Non-linear Least Square Curve Fitting. . . . . . . . . . . . . . 102
6.4.13 Comparison of Coated Sensor and ISE . . . . . . . . . . . . . 102
6.5 Results and Discussions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
6.5.1 Sorption Studies. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
6.5.2 Uptake Kinetics Studies . . . . . . . . . . . . . . . . . . . . . . . . 103
6.5.3 Study of Selectivity Test. . . . . . . . . . . . . . . . . . . . . . . . 104
6.5.4 pH-Dependent Binding Profile . . . . . . . . . . . . . . . . . . . 106
6.5.5 Calibration Standard. . . . . . . . . . . . . . . . . . . . . . . . . . . 106
6.5.6 Unknown Sample Measurement . . . . . . . . . . . . . . . . . . 107
6.5.7 Reusability of the Sensor . . . . . . . . . . . . . . . . . . . . . . . 108
